Chloromethylation of anthanthrone and Threne Gold Yellow GK in concentrated sulfuric acid or aluminum chloride-pyridine solution and sym-dichlorodimethyl ether gave bis- and tetrachloromethylated anthanthrone, and a monochloromethylated Threne Gold Yellow GK. These chloromethylated compounds were derived into reduction products by use of hydrosulfide, their pyridinium salts and isothiuronium salts were synthesized, and their dyeing abilities have been investigated.
4, 4'- and 3, 3'-Dibenzoanthronyls were chloromethylated by use of concentrated sulfuric acid and sym-dichlorodimethyl ether to obtain each of their bis-chloro methylated compound, respectively. These dibenzoanthronyls and their chloro methylated compounds were oxidatively decomposed with chromic acid and several kinds of decomposition product were obtained depending on the extent of oxidation. By studying the structure of these compounds, it was confirmed that the chloromethyl group enters into 9, 9'-position. Syntheses of pyridinium salt and isothiuronium salt were made to give watersoluble dyes and their cyclization gave benzoanthrone type vat dyes. Their properties, especially of their dyeing qualities, have been clarified.
Syntheses of several dyes having carbazide group, -CON3, have been made by use of the following method. Reaction of 1 mole p-, m- or o-aminobenzhydrazide, 2 moles sodium nitrite, and hydrochloric acid gave carbazide benzenediazonium chloride and coupling of this with various coupling agents gave dyes. The aqueous solution of these dyes in the presence of sodium chloride was used for dyeing of cellulosic fiber at room temperature, then an addition of sodium carbonate gave an ester-like binding as indicated in equation (1) by the reaction of OH group in cellulose: D-CON3+HO-Cellulose D-COO-Cellulose + NH3(1) where D = dye matrix having sulfonyl group. On the other hand, heating of dyed product in a neutral or weakly acidic solution gave a dye molecule of urethan combination as shown in equation (2) from OH group of cellulose fiber: D-CON3 D-N=C=O + N22 D-N=C=O + HO-Cellulose → D-NHC00-Cellulose (2) A group of these dyes was named as a diact Color “C” by the author.
p-Sulfazidebenzenediazonium chloride, obtained by treatment of 1 mole of paminobezenesulfohydrazide with 2 moles sodium nitrite and hydrochloric acid, was used for coupling with various coupling agents for syntheses of water-soluble and water-insoleble dyes having sulfonylazide grop (-S02N3). Also, various dyes were chlorosulf onated and their subsequent reaction with sodium azide to give a dispersed reactive dye having -S02N3 group. Water-soluble dyes among these compounds combine with cellulose fiber in the presence of sodium carbonate as follows: D-SO2N3 + HO-Cellulose D-SO2O-Cellulose + NH3 Dyeing of Nylon with aqueous dispersion of water-insoluble dispersion type dyes gave the reaction with terminal amino group in the Nylon fiber . Discussions were made on the dyeing ability and fastness of these dyes .